This invention relates to flexible graphite sheet that exhibits increased isotropy as compared with prior art flexible graphite sheet. More particularly, the present invention relates to a flexible graphite sheet having increased isotropy for forming gaskets as well as the components of an electrochemical fuel cell, including fluid flow field plates, seals and gas diffusion layers therefor.
Graphites are made up of layer planes of hexagonal arrays or networks of carbon atoms. These layer planes of hexagonally arranged carbon atoms are substantially flat and are oriented or ordered so as to be substantially parallel and equidistant to one another. The substantially flat, parallel equidistant sheets or layers of carbon atoms, usually referred to as basal planes, are linked or bonded together and groups thereof are arranged in crystallites. Highly ordered graphites consist of crystallites of considerable size: the crystallites being highly aligned or oriented with respect to each other and having well ordered carbon layers. In other words, highly ordered graphites have a high degree of preferred crystallite orientation. It should be noted that graphites exhibit anisotropy because of their inherent structure and thus exhibit or possess many properties that are highly directional, especially thermal and electrical conductivity and fluid diffusion. Briefly, graphites may be characterized as laminated structures of carbon, that is, structures consisting of superposed layers or laminae of carbon atoms joined together by weak van der Waals forces. In considering the graphite structure, two axes or directions are usually noted, to wit, the xe2x80x9ccxe2x80x9d axis or direction and the xe2x80x9caxe2x80x9d axes or directions. For simplicity, the xe2x80x9ccxe2x80x9d axis or direction may be considered as the direction perpendicular to the carbon layers. The xe2x80x9caxe2x80x9d axes or directions may be considered as the directions parallel to the carbon layers or the directions perpendicular to the xe2x80x9ccxe2x80x9d direction. The natural graphites suitable for manufacturing flexible graphite possess a very high degree of orientation.
As noted above, the bonding forces holding the parallel layers of carbon atoms together are only weak van der Waals forces. Graphites can be treated so that the spacing between the superposed carbon layers or laminae can be appreciably opened up so as to provide a marked expansion in the direction perpendicular to the layers, that is, in the xe2x80x9ccxe2x80x9d direction and thus form an expanded or intumesced graphite structure in which the laminar character of the carbon layers is substantially retained.
Natural graphite flake which has been greatly expanded and more particularly expanded so as to have a final thickness or xe2x80x9ccxe2x80x9d direction dimension which is at least about 80 or more times the original xe2x80x9ccxe2x80x9d direction dimension can be formed without the use of a binder into cohesive or integrated flexible graphite sheets of expanded graphite, e.g. webs, papers, strips, tapes, or the like. The formation of graphite particles which have been expanded to have a final thickness or xe2x80x9ccxe2x80x9d dimension which is at least about 80 times the original xe2x80x9ccxe2x80x9d direction dimension into integrated flexible sheets by compression, without the use of any binding material is believed to be possible due to the excellent mechanical interlocking, or cohesion which is achieved between the voluminously expanded graphite particles.
In addition to flexibility, the sheet material, as noted above, has also been found to possess a high degree of anisotropy with respect to thermal and electrical conductivity and fluid diffusion, comparable to the natural graphite starting material due to orientation of the expanded graphite particles substantially parallel to the opposed faces of the sheet resulting from very high compression, e.g. roll pressing. Sheet material thus produced has excellent flexibility, good strength and a very high degree of orientation.
Briefly, the process of producing flexible, binderless anisotropic graphite sheet material, such as web, paper, strip, tape, foil, mat, or the like, comprises compressing or compacting under a predetermined load and in the absence of a binder, expanded graphite particles which have a xe2x80x9ccxe2x80x9d direction dimension which is at least about 80 times that of the original particles so as to form a substantially flat, flexible, integrated graphite sheet. The expanded graphite particles, which generally are worm-like or vermiform in appearance, once compressed, will maintain the compression set and alignment with the opposed major surfaces of the sheet. The density and thickness of the sheet material can be varied by controlling the degree of compression. The density of the sheet material can be within the range of from about 0.08 grams per cubic centimeters (g/cc) to about 2.0 g/cc. The flexible graphite sheet material exhibits an appreciable degree of anisotropy due to the alignment of graphite particles parallel to the major opposed, parallel surfaces of the sheet, with the degree of anisotropy increasing upon roll pressing of the sheet material to increased density. In roll pressed anisotropic sheet material, the thickness, i.e. the direction perpendicular to the opposed, parallel sheet surfaces comprises the xe2x80x9ccxe2x80x9d direction and the directions ranging along the length and width, i.e. along or parallel to the opposed, major surfaces comprises the xe2x80x9caxe2x80x9d directions and the thermal, electrical and fluid diffusion properties of the sheet are very different, by orders of magnitude, for the xe2x80x9ccxe2x80x9d and xe2x80x9caxe2x80x9d directions.
This very considerable difference in properties, known as anisotropy, which is directionally dependent, can be disadvantageous in some applications. For example, in gasket applications where flexible graphite sheet is used as the gasket material and in use is held tightly between metal surfaces, the diffusion of fluid, e.g. gases or liquids, occurs more readily parallel to and between the major surfaces of the flexible graphite sheet. It would, in most instances, provide for greater gasket performance, if the resistance to fluid flow parallel to the major surfaces of the graphite sheet (xe2x80x9caxe2x80x9d direction) were increased, even at the expense of reduced resistance to fluid diffusion flow transverse to the major faces of the graphite sheet (xe2x80x9ccxe2x80x9d direction). With respect to electrical properties, the resistivity of anisotropic flexible graphite sheet is high in the direction transverse to the major surfaces (xe2x80x9ccxe2x80x9d direction) of the flexible graphite sheet, and very substantially less in the direction parallel to and between the major faces of the flexible graphite sheet (xe2x80x9caxe2x80x9d direction). In applications such as fluid flow field plates, seals and gas diffusion layers for fuel cells, it would be of advantage if the electrical resistance transverse to the major surfaces of the flexible graphite sheet (xe2x80x9ccxe2x80x9d direction) were decreased, even at the expense of an increase in electrical resistivity in the direction parallel to the major faces of the flexible graphite sheet (xe2x80x9caxe2x80x9d direction).
With respect to thermal properties, the thermal conductivity of a flexible graphite sheet in a direction parallel to the upper and lower surfaces of the flexible graphite sheet is relatively high, while it is relatively very low in the xe2x80x9ccxe2x80x9d direction transverse to the upper and lower surfaces.
The foregoing situations are accommodated by the present invention.
A method for making flexible graphite sheet, which includes treating graphite flake sized such that no more than about 30% by weight does not pass through an 80 mesh screen (referred to as +80 mesh) (unless otherwise indicated, all references to mesh sizes herein are to U.S. standard screens) with an intercalating solution to obtain heat expandable, intercalated graphite flake; exposing the graphite flake to an elevated temperature to exfoliate the flake into expanded particles of graphite; and passing the expanded particles of graphite through pressure rolls to form a compressed sheet formed of said blended mixture, the compressed sheet having opposed major surfaces. In other words, the graphite flake employed is sized such that at least about 70% by weight passes through an 80 mesh screen. The graphite flake most useful in the invention is sized such that at least about 50% by weight passes through an 80 mesh screen but not a 140 mesh screen (referred to as 80xc3x97140 mesh) and has a moisture content of no greater than about 1.0%.
In a preferred embodiment of the invention, transverse fluid channels are formed in the compressed sheet by mechanically impacting a surface of the sheet to displace graphite within the sheet at a plurality of predetermined locations, and at least one groove is formed in at least one of the surfaces of the sheet by mechanically impacting an opposed surface of the sheet.
The invention also comprises a flexible graphite sheet made in accordance with the inventive process, itself and as a sealing gasket or an electrode component of a membrane electrode assembly comprising a pair of electrodes and an ion exchange membrane positioned between the electrodes.